The present invention relates to a novel oxidation polymer of a substituted phenol.
Conventionally, for an oxidation polymer of a substituted phenol, though concern has been concentrated mainly on oxidation polymers of 2,6-di-substituted phenols, recently, there is also a notice on oxidation polymers of phenols having no substituent at the 2- and/or the 6-position (Kagaku to Kogyo, vol. 53, no. 4, pp. 501 to 505 (2000)).
On the other hand, aromatic polymers carrying a saturated hydrocarbon group having a large number of carbon atoms have been developed, and various characteristics have been found regarding the crystallinity, liquid crystallinity, viscoelasticity, solubility, and the like, of the polymers. In Macromolecules, 29, 1337, (1996), aromatic polyesters as described above are described, and in Macromolecules, 27, 7754 (1994), polyanilines as described above are described.
However, regarding the oxidation polymers of phenols including no substituent on the 2- and/or the 6-position having a saturated hydrocarbon group with a large number of carbon atoms, only an oxidation polymer of nonylphenol has been reported (J. Electroamal. Chem., 290, 79 (1990)), and there is no description of the crystallinity of this polymer. Further, also regarding oxidation polymers of 2,6-di-substituted phenols carrying a saturated hydrocarbon substituent having a large number of carbon atoms, only those carrying a substituent having 14 or less carbon atoms, such as an oxidation polymer of 2-methyl-6-tetradecylphenol (J. Polym. Sci. Part A-1, 9, 2361 (1971)), an oxidation polymer of 2-methyl-6-(2-tetradecyl)phenol (Macromolecules, 5, 676 (1972)) and the like, have been reported, and there is also no description regarding crystallinity thereof.
In poly(1,4-phenylene oxide) and poly(2,5-dimethyl-1,4-phenylene oxide), which are oxidation polymers of a phenol including no substitution on the 2- and/or the 6-position, the crystal melting point derived from the main chain is observed even after melting-cooling, while in poly(2,6-dimethyl-1,4-phenylene oxide), the crystal melting point is not detected at all after melting-cooling (Kagaku to Kogyo, vol. 53, no. 4, pp. 501 to 505 (2000)). Namely, in general, it may be guessed that the oxidation polymers of 2,6-di-substituted phenols do not cause crystallization easily, and crystallization does not occur even if the number of carbon atoms of a substituent is 14.
The present invention is an oxidation polymer of a substituted phenol, which is obtained by oxidative polymerization of at least one substituted phenol compound selected from the group consisting of a substituted phenol compound represented by the following formula (Ia), and a 2,6-di-substituted phenol compound represented by the following formula (Ib), wherein the oxidation polymer has a number-average degree of polymerization of 3 or more: 
wherein, in formula (Ia), R1, R2, R3, and R4 each individually represent a hydrogen atom, a substituted or unsubstituted hydrocarbon group, a substituted or unsubstituted hydrocarbon oxy group, a substituted or unsubstituted amino group, a substituted or unsubstituted mercapto group, or a halogen atom; R1 and R2, R2 and R3, or R3 and R4 may form a ring; provided that at least one of R1 to R4 represents a substituted or unsubstituted, saturated hydrocarbon group having 10 or more carbon atoms, and R1 and/or R4 represent a hydrogen atom; and 
wherein, in formula (Ib), R11 represents a substituted or unsubstituted, saturated hydrocarbon group having 15 or more carbon atoms, and R12 is the same group as R11, or when R12 is different from R11, R12 represents a substituted or unsubstituted hydrocarbon group, a substituted or unsubstituted hydrocarbon oxy group, a substituted or unsubstituted amino group, a substituted or unsubstituted mercapto group, or a halogen atom.
Further, the present invention is an oxidation polymer of a substituted phenol, which is obtained by oxidative polymerization of at least one substituted phenol compound selected from the group consisting of a substituted phenol compound represented by the formula (Ia), and a 2,6-di-substituted phenol compound represented by the formula (Ib), wherein the oxidation polymer has a number-average degree of polymerization of 3 or more, and a crystal melting point of 5 J/g or more, xe2x88x92100xc2x0 C. or higher and less than 300xc2x0 C.: 
wherein, in formula (Ia), R1, R2, R3, and R4 each individually represent a hydrogen atom, a substituted or unsubstituted hydrocarbon group, a substituted or unsubstituted hydrocarbon oxy group, a substituted or unsubstituted amino group, a substituted or unsubstituted mercapto group, or a halogen atom; R1 and R2, R2 and R3, or R3 and R4 may form a ring; provided that at least one of R1 to R4 represents a substituted or unsubstituted, saturated hydrocarbon group having 10 or more carbon atoms, and R1 and/or R4 represent a hydrogen atom; and 
wherein R11 represents a substituted or unsubstituted, saturated hydrocarbon group having 15 or more carbon atoms (preferably having 16 or more carbon atoms), and R12 is the same group as R11, or when R12 is different from R11, R12 represents a substituted or unsubstituted hydrocarbon group, a substituted or unsubstituted hydrocarbon oxy group, a substituted or unsubstituted amino group, a substituted or unsubstituted mercapto group, or a halogen atom.
Other and further features, and advantages of the invention will appear more fully from the following description.
The oxidation polymer of a substituted phenol of the present invention is an oxidation polymer, which is obtained by oxidative polymerization of at least one compound selected from the group consisting of a substituted phenol compound represented by the formula (Ia), and a 2,6-di-substituted phenol compound represented by the formula (Ib), wherein the oxidation polymer has a number-average polymerization degree of 3 or more.
The substituted phenol compounds represented by the formula (Ia) are explained below.
When R1 to R4 in the above-mentioned formula (Ia) represent a hydrocarbon group, it is preferably an alkyl group having 1 to 100 carbon atoms (more preferably having 1 to 50 carbon atoms), a cycloalkyl group having 3 to 100 carbon atoms (more preferably having 3 to 50 carbon atoms), an aralkyl group having 7 to 30 carbon atoms (more preferably having 7 to 20 carbon atoms, particularly preferably having 7 to 9 carbon atoms) or an aryl group having 6 to 30 carbon atoms (more preferably having 6 to 20 carbon atoms, particularly preferably having 6 to 9 carbon atoms). Specific examples thereof include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, t-butyl group, pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, octyl group, nonyl group, benzyl group, 2-phenylethyl group, 1-phenylethyl group, phenyl group, 4-methylphenyl group, 4-ethylphenyl group, and the like.
When R1 to R4 in the above-mentioned formula (Ia) represent a substituted hydrocarbon group, it is preferably an alkyl group having 1 to 100 carbon atoms (more preferably having 1 to 50 carbon atoms), a cycloalkyl group having 3 to 100 carbon atoms (more preferably having 3 to 50 carbon atoms), an aralkyl group having 7 to 30 carbon atoms (more preferably having 7 to 20 carbon atoms, particularly preferably having 7 to 9 carbon atoms), or an aryl group having 6 to 30 carbon atoms (more preferably having 6 to 20 carbon atoms, particularly preferably having 6 to 9 carbon atoms), each of which is substituted by a halogen atom, a hydroxyl group, an alkoxy group, an amino group, a substituted amino group, and the like. Specific examples thereof include a trifluoromethyl group, 2-t-butyloxyethyl group, 3-dimethylaminopropyl group, and the like.
When R1 to R4 in the above-mentioned formula (Ia) represent a hydrocarbon oxy group, it is preferably an alkoxy group having 1 to 30 carbon atoms (more preferably having 1 to 20 carbon atoms, particularly preferably having 1 to 9 carbon atoms), a cycloalkoxy group having 3 to 30 carbon atoms (more preferably having 3 to 20 carbon atoms, particularly preferably having 3 to 9 carbon atoms), an aralkyloxy group having 7 to 30 carbon atoms (more preferably having 7 to 20 carbon atoms, particularly preferably having 7 to 9 carbon atoms), or an aryloxy group having 6 to 30 carbon atoms (more preferably having 6 to 20 carbon atoms, particularly preferably having 6 to 9 carbon atoms). Specific examples thereof include methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, iso-butoxy group, t-butoxy group, pentyloxy group, cyclopentyloxy group, hexyloxy group, cyclohexyloxy group, octyloxy group, nonyloxy group, benzyloxyl group, 2-phenylethoxy group, 1-phenylethoxy group, phenyloxy group, 4-methylphenyloxy group, 4-ethylphenyloxy group, and the like.
When R1 to R4 in the above-mentioned formula (Ia) represent a substituted hydrocarbon oxy group, it is preferably an alkoxy group having 1 to 30 carbon atoms (more preferably having 1 to 10 carbon atoms, further preferably having 1 to 9 carbon atoms), a cycloalkoxy group having 3 to 30 carbon atoms (more preferably having 3 to 20 carbon atoms, particularly preferably having 3 to 9 carbon atoms), an aralkyloxy group having 7 to 30 carbon atoms (more preferably having 7 to 20 carbon atoms, particularly preferably having 7 to 9 carbon atoms), or an aryloxy group having 6 to 30 carbon atoms (more preferably having 6 to 20 carbon atoms, particularly preferably having 6 to 9 carbon atoms), each of which is substituted by a halogen atom, an alkoxy group, an amino group, a substituted amino group, and the like. Specific examples thereof include trifluoromethoxy group, 2-t-buthyloxyethoxy group, 3-dimethylaminopropoxy group, and the like.
When R1 to R4 in the above-mentioned formula (Ia) represent a substituted amino group, it is preferably an amino group substituted by an alkyl group having 1 to 30 carbon atoms (more preferably having 1 to 20 carbon atoms), a cycloalkyl group having 3 to 30 carbon atoms (more preferably having 3 to 20 carbon atoms), an aralkyl group having 7 to 30 carbon atoms (more preferably having 7 to 20 carbon atoms), or an aryl group having 6 to 30 carbon atoms (more preferably having 6 to 20 carbon atoms). Specific examples thereof include methylamino group, dimethylamino group, diethylamino group, di-n-propylamino group, di-iso-propylamino group, di-n-butylamino group, di-iso-butylamino group, di-t-butylamino group, dipentylamino group, dicyclopentylamino group, dihexylamino group, dicyclohexylamino group, dioctylamino group, dinonylamino group, dibenzylamino group, di-2-phenylethylamino group, di-1-phenylethylamino group, diphenylamino group, di-4-methylphenylamino group, di-4-ethylphenylamino group, and the like.
When R1 to R4 in the above-mentioned formula (Ia) represent a substituted mercapto group, it is preferably an alkylmercapto group having 1 to 30 carbon atoms (more preferably having 1 to 20 carbon atoms), a cycloalkylmercapto group having 3 to 30 carbon atoms (more preferably having 3 to 20 carbon atoms), an aralkylmercapto group having 7 to 30 carbon atoms (more preferably having 7 to 20 carbon atoms), or an arylmercapto group having 6 to 30 carbon atoms (more preferably having 6 to 20 carbon atoms). Specific examples thereof include methylmercapto group, ethylmercapto group, n-propylmercapto group, iso-propylmercapto group, n-butylmercapto group, iso-butylmercapto group, t-butylmercapto group, pentylmercapto group, cyclopentylmercapto group, hexylmercapto group, cyclohexylmercapto group, octylmercapto group, nonylmercapto group, benzylmercapto group, 2-phenylethylmercapto group, 1-phenylethylmercapto group, phenylmercapto group, 4-methylphenylmercapto group, 4-ethylphenylmercapto group, and the like.
When R1 to R4 in the above-mentioned formula (Ia) represent a halogen atom, it is a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, more preferably a fluorine atom, a chlorine atom, or a bromine atom, further preferably a fluorine atom or a chlorine atom.
Regarding R1 to R4 in the above-mentioned formula (Ia), when R1 and R2, R2 and R3, or R3 and R4 form a ring, it is preferably a 5- to 7-membered ring, and it is more preferably that R1 and R2, R2 and R3, or R3 and R4 each form xe2x80x94(CH2)3xe2x80x94 group, xe2x80x94(CH2)4xe2x80x94 group, or xe2x80x94CHxe2x95x90CHxe2x80x94CHxe2x95x90CHxe2x80x94 group constituting a ring.
At least one group of R1 to R4 in the above-mentioned formula (Ia), is a substituted or unsubstituted, saturated hydrocarbon group having 10 or more carbon atoms. The number of substitution of these groups is from 1 to 3, preferably 1 to 2, more preferably 1.
The number of carbon atoms of an unsubstituted saturated hydrocarbon group as at least one group of R1 to R4 in the above-mentioned formula (Ia), is preferably from 10 to 100, more preferably from 10 to 50, further preferably from 12 to 30, particularly preferably from 15 to 22. The above-mentioned saturated hydrocarbon group is preferably an alkyl group or a cycloalkyl group, more preferably an alkyl group, further preferably xe2x80x94(CH2)n-1CH3 or xe2x80x94CH(CH3)(CH2)n-3CH3 (wherein n represents the number of carbon atoms).
The substituted saturated hydrocarbon group as at least one group of R1 to R4 in the above-mentioned formula (Ia), is preferably the above-mentioned saturated hydrocarbon group substituted by a halogen atom, a hydroxyl group, an alkoxy group, an amino group, a substituted amino group, and the like, more preferably the above-mentioned saturated hydrocarbon group substituted by a fluorine atom.
At least one group of R1 to R4 in the above-mentioned formula (Ia), is preferably a saturated hydrocarbon group.
In R1, R2 and R4 in the above-mentioned formula (Ia), as another group other than the substituent having 10 or more carbon atoms, it is preferably a hydrogen atom, a hydrocarbon group having 1 to 9 carbon atoms, a hydrocarbon oxy group having 1 to 9 carbon atoms, or a halogen atom. It is more preferably a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, further preferably a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, particularly preferably a hydrogen atom or methyl group. In R3 in the above-mentioned formula (Ia), as another group other than the substituent having 10 or more carbon atoms, it is preferably a hydrogen atom, a hydrocarbon group having 1 to 9 carbon atoms, a hydrocarbon oxy group having 1 to 9 carbon atoms, or a halogen atom. It is more preferably a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a hydrocarbon oxy group having 1 to 6 carbon atoms, further preferably a hydrogen atom or a phenoxy group, particularly preferably a hydrogen atom.
Next, the 2,6-di-substituted phenol compound represented by the formula (Ib) is described below.
In the above-mentioned formula (Ib), R11 represents a substituted or unsubstituted, saturated hydrocarbon group having 15 or more carbon atoms.
The number of carbon atoms of a saturated hydrocarbon group R11 in the above-mentioned formula (Ib), is generally 15 or more, preferably from 15 to 100, more preferably from 16 to 50, further preferably from 18 to 30, particularly preferably from 18 to 22. The above-mentioned saturated hydrocarbon group is preferably an alkyl group or a cycloalkyl group, more preferably an alkyl group, further preferably xe2x80x94(CH2)n-1CH3 or xe2x80x94CH(CH3)(CH2)n-3CH3 (wherein n represents the number of carbon atoms).
The substituted saturated hydrocarbon group as R11 in the above-mentioned formula (Ib) is preferably the above-mentioned saturated hydrocarbon group substituted by a halogen atom, a hydroxyl group, an alkoxy group, an amino group, a substituted amino group, and the like, more preferably the above-mentioned saturated hydrocarbon group substituted by a fluorine atom.
R11 in the above-mentioned formula (Ib) is preferably an unsubstituted saturated hydrocarbon group.
In the above-mentioned formula (Ib), R12 is the same group as R11, or when R12 is different from R11, R12 represents a substituted or unsubstituted hydrocarbon group, a substituted or unsubstituted hydrocarbon oxy group, a substituted or unsubstituted amino group, a substituted or unsubstituted mercapto group, or a halogen atom.
When R12 is different from R11, the hydrocarbon group as R12 in the above-mentioned formula (Ib) is preferably an alkyl group having 1 to 30 carbon atoms (further preferably having 1 to 22 carbon atoms), a cycloalkyl group having 3 to 30 carbon atoms (further preferably having 3 to 22 carbon atoms), an aralkyl group having 7 to 30 carbon atoms (further preferably having 7 to 22 carbon atoms), or an aryl group having 6 to 30 carbon atoms (further preferably having 6 to 22 carbon atoms), and specifically, the above-mentioned substituents are listed.
When R12 is different from R11, the substituted hydrocarbon group as R12 in the above-mentioned formula (Ib) is preferably an alkyl group having 1 to 30 carbon atoms (further preferably having 1 to 22 carbon atoms), a cycloalkyl group having 3 to 30 carbon atoms (further preferably having 3 to 22 carbon atoms), an aralkyl group having 7 to 30 carbon atoms (further preferably having 7 to 22 carbon atoms), or an aryl group having 6 to 30 carbon atoms (further preferably having 6 to 22 carbon atoms), each of which is substituted by a halogen atom, an alkoxy group, an amino group, a substituted amino group, and the like, and specifically, the above-mentioned substituents are listed.
The hydrocarbon oxy group as R12 in the above-mentioned formula (Ib) is preferably an alkoxy group having 1 to 30 carbon atoms (further preferably having 1 to 20 carbon atoms), a cycloalkoxy group having 3 to 30 carbon atoms (further preferably having 3 to 20 carbon atoms), an aralkyloxy group having 7 to 30 carbon atoms (further preferably having 7 to 20 carbon atoms), or an aryloxy group having 6 to 30 carbon atoms (further preferably having 6 to 20 carbon atoms), and specifically, the above-mentioned substituents are listed.
The substituted hydrocarbon oxy group as R12 in the above-mentioned formula (Ib) is preferably an alkoxy group having 1 to 30 carbon atoms (further preferably having 3 to 20 carbon atoms), a cycloalkoxy group having 3 to 30 carbon atoms (further preferably having 3 to 20 carbon atoms), an aralkyloxy group having 7 to 30 carbon atoms (further preferably having 7 to 20 carbon atoms), or an aryloxy group having 6 to 30 carbon atoms (further preferably having 6 to 20 carbon atoms), each of which is substituted by a halogen atom, an alkoxy group, an amino group, a substituted amino group, and the like, and specifically, the above-mentioned substituents are listed.
The substituted amino group as R12 in the above-mentioned formula (Ib) is preferably an alkyl group having 1 to 30 carbon atoms (further preferably having 1 to 20 carbon atoms), a cycloalkyl group having 3 to 30 carbon atoms (further preferably having 3 to 20 carbon atoms), an aralkyl group having 7 to 30 carbon atoms (further preferably having 7 to 20 carbon atoms), or an aryl group having 6 to 30 carbon atoms (further preferably having 6 to 20 carbon atoms), and specifically, the above-mentioned substituents are listed.
The substituted mercapto group as R12 in the above-mentioned formula (Ib) is preferably an alkylmercapto group having 1 to 30 carbon atoms (further preferably having 1 to 20 carbon atoms), a cycloalkylmercapto group having 3 to 30 carbon atoms (further preferably having 3 to 20 carbon atoms), an aralkylmercapto group having 7 to 30 carbon atoms (further preferably having 7 to 20 carbon atoms), or an arylmercapto group having 6 to 30 carbon atoms (further preferably having 6 to 20 carbon atoms), and specifically, the above-mentioned substituents are listed.
The halogen atom as R12 in the above-mentioned formula (Ib) is a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, preferably a fluorine atom, a chlorine atom, or a bromine atom, more preferably a fluorine atom or a chlorine atom.
When R12 is different from R11, R12 in the above-mentioned formula (Ib) is preferably a hydrocarbon group having 1 to 9 carbon atoms, a hydrocarbon oxy group having 1 to 9 carbon atoms, or a halogen atom, more preferably a hydrocarbon group having 1 to 9 carbon atoms or a hydrocarbon oxy group having 1 to 9 carbon atoms, further preferably a hydrocarbon group having 1 to 9 carbon atoms, particularly preferably a hydrocarbon group having 1 to 6 carbon atoms.
The polymer of the present invention may be obtained by oxidative polymerization of a substituted phenol compound represented by the above-mentioned formula (Ia) used alone or in admixture thereof, or it may be obtained by oxidative polymerization of a 2,6-disubstituted phenol compound represented by the above-mentioned formula (Ib) used alone or in admixture thereof. Alternatively, the polymer of the present invention may be obtained by oxidative polymerization of one or more kinds of the compound represented by the above-mentioned formula (Ia), together with one or more kinds of the compound represented by the above-mentioned formula (Ib). Further, the polymer of the present invention may be obtained by oxidative polymerization of a compound represented by the above-mentioned formula (Ia) and/or a compound represented by the above-mentioned formula (Ib), together with a phenol compound represented by the following formula (II), a phenol compound represented by the following formula (III), and/or a bis-phenol compound represented by the following formula (IV). 
In the formulae (II), (III), and (IV), each of R5 is independently a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 9 carbon atoms, a substituted or unsubstituted hydrocarbon oxy group having 1 to 9 carbon atoms, an amino group, a substituted amino group having 1 to 9 carbon atoms, a mercapto group, a substituted mercapto group having 1 to 9 carbon atoms, or a halogen atom, and two adjacent R5 may form a ring. R6 represents an oxygen atom, a sulfur atom, a divalent hydrocarbon group, or a divalent substituted hydrocarbon group, and m is 1 or 0.
The hydrocarbon group as R5 in the above-mentioned formulae (II) to (IV), represents preferably an alkyl group having 1 to 9 carbon atoms, a cycloalkyl group having 3 to 9 carbon atoms, an aralkyl group having 7 to 9 carbon atoms, or an aryl group having 6 to 9 carbon atoms. Specific examples thereof include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, t-butyl group, pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, octyl group, nonyl group, benzyl group, 2-phenylethyl group, 1-phenylethyl group, phenyl group, 4-methylphenyl group, 4-ethylphenyl group, and the like.
The substituted hydrocarbon group as R5 in the above-mentioned formulae (II) to (IV), represents preferably an alkyl group having 1 to 9 carbon atoms, a cycloalkyl group having 3 to 9 carbon atoms, an aralkyl group having 7 to 9 carbon atoms, or an aryl group having 6 to 9 carbon atoms, each of which is substituted with a halogen atom, an alkoxy group, an amino group, a substituted amino group, and the like. Specific examples thereof include trifluoromethyl group, 2-t-butyloxyethyl group, 3-dimethylaminopropyl group, and the like.
The hydrocarbon oxy group as R5 in the above-mentioned formulae (II) to (IV), represents preferably an alkoxy group having 1 to 9 carbon atoms, a cycloalkoxy group having 3 to 9 carbon atoms, an aralkyloxy group having 7 to 9 carbon atoms, or an aryloxy group having 6 to 9 carbon atoms. Specific examples thereof include a methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, iso-butoxy group, t-butoxy group, pentyloxy group, cyclopentyloxy group, hexyloxy group, cyclohexyloxy group, octyloxy group, nonyloxy group, benzyloxy group, 2-phenylethoxy group, 1-phenylethoxy group, phenyloxy group, 4-methylphenyloxy group, 4-ethylphenyloxy group, and the like.
The substituted hydrocarbon oxy group as R5 in the above-mentioned formulae (II) to (IV), represents preferably an alkoxy group having 1 to 9 carbon atoms, a cycloalkoxy group having 3 to 9 carbon atoms, an aralkyloxy group having 7 to 9 carbon atoms, or an aryloxy group having 6 to 9 carbon atoms, each of which is substituted by a halogen atom, an alkoxy group, an amino group, a substituted amino group, and the like. Specific examples thereof include trifluoromethoxy group, 2-t-butyloxyethoxy group, 3-dimethylaminopropoxy group, and the like.
The substituted amino group as R5 in the above-mentioned formulae (II) to (IV), represents preferably an amino group substituted by an alkyl group having 1 to 9 carbon atoms, a cycloalkyl group having 3 to 9 carbon atoms, an aralkyl group having 7 to 9 carbon atoms, or an aryl group having 6 to 9 carbon atoms. Specific examples thereof include methylamino group, dimethylamino group, diethylamino group, di-n-propylamino group, di-iso-propylamino group, di-n-butylamino group, di-iso-butylamino group, di-t-butylamino group, pentylamino group, cyclopentylamino group, hexylamino group, cyclohexylamino group, octylamino group, nonylamino group, benzylamino group, 2-phenylethylamino group, 1-phenylethylamino group, phenylamino group, 4-methylphenylamino group, 4-ethylphenylamino group, and the like.
The substituted mercapto group as R5 in the above-mentioned formulae (II) to (IV), is preferably an alkylmercapto group having 1 to 9 carbon atoms, a cycloalkylmercapto group having 3 to 9 carbon atoms, an aralkylmercapto group having 7 to 9 carbon atoms, or an arylmercapto group having 6 to 9 carbon atoms. Specific examples thereof include methylmercapto group, ethylmercapto group, n-propylmercapto group, iso-propylmercapto group, n-butylmercapto group, iso-butylmercapto group, t-butylmercapto group, pentylmercapto group, cyclopentylmercapto group, hexylmercapto group, cyclohexylmercapto group, octylmercapto group, nonylmercapto group, benzylmercapto group, 2-phenylethylmercapto group, 1-phenylethylmercapto group, phenylmercapto group, 4-methylphenylmercapto group, 4-ethylphenylmercapto group, and the like.
The halogen atom as R5 in the above-mentioned formulae (II) to (IV), is fluorine atom, chlorine atom, bromine atom, or iodine atom, more preferably fluorine atom, chlorine atom, or bromine atom, further preferably fluorine atom or chlorine atom.
When two adjacent R5""s in the above-mentioned formulae (II) to (IV), form a ring, the ring is preferably a 5- to 7-membered ring, and it is further preferable that two adjacent R5""s form xe2x80x94(CH2)3xe2x80x94 group, xe2x80x94(CH2)4xe2x80x94 group, or xe2x80x94CHxe2x95x90CHxe2x80x94CHxe2x95x90CHxe2x80x94 group constituting a ring.
R5 in the above-mentioned formulae (II) to (IV), is preferably a hydrogen atom, a hydrocarbon group having 1 to 9 carbon atoms, a hydrocarbon oxy group having 1 to 9 carbon atoms, or a halogen atom, more preferably a hydrogen atom, a hydrocarbon group having 1 to 9 carbon atoms, or a hydrocarbon oxy group having 1 to 9 carbon atoms, further preferably a hydrogen atom or a hydrocarbon group having 1 to 9 carbon atoms, particularly preferably a hydrogen atom or hydrocarbon group having 1 to 6 carbon atoms.
The divalent hydrocarbon group as R6 in the above-mentioned formula (IV), is preferably an alkylene group having 1 to 9 carbon atoms, an aralkylene group having 7 to 9 carbon atoms, or an arylene group having 6 to 9 carbon atoms. Specific examples thereof include methylene group, 1,1-ethylene group, 1,2-ethylene group, 1,1-propylene group, 1,3-propylene group, 2,2-propylene group, 1,1-butylene group, 2,2-butylene group, 3-methyl-2,2-butylene group, 3,3-dimethyl-2,2-butylene group, 1,1-pentylene group, 3,3-pentylene group, 1,1-hexylene group, 1,1-heptylene group, 1,1-octylene group, 1,1-nonylene group, 1,1-cyclopentylene group, 1,1-cyclohexylene group, phenylmethylene group, 1-phenyl-1,1-ethylene group, 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group, and the like.
The divalent substituted hydrocarbon group as R6 in the above-mentioned formula (IV), is preferably an alkylene group having 1 to 9 carbon atoms, an aralkylene group having 7 to 9 carbon atoms, or an arylene group having 6 to 9 carbon atoms, each of which is substituted by a halogen atom, an alkoxy group, di-substituted amino group, and the like. Specific examples thereof include hexafluoro-2,2-propylene group, pentafluorophenylmethylene group, 4-methoxyphenylmethylene group, 4-dimethylaminophenylmethylene group, and the like.
R6 in the above-mentioned formula (IV), is preferably an oxygen atom or a divalent hydrocarbon group, more preferably an alkylene group having 1 to 9 carbon atoms or an aralkylene group having 7 to 9 carbon atoms, further preferably an alkylene group having 1 to 6 carbon atoms.
When a substituted phenol compound represented by the above-mentioned formula (Ia) and/or a 2,6-di-substituted phenol compound represented by the above-mentioned formula (Ib), are used together with a phenol compound represented by the above-mentioned formula (II), a phenol compound represented by the above-mentioned formula (III), and/or a bis-phenol compound represented by the above-mentioned formula (IV), the ratio thereof is appropriately determined within a range in which physical properties of the intended polymer are not deteriorated. The proportion of the above-mentioned substituted phenol (the total amount of a compound represented by the formula (Ia) and/or a compound represented by the formula (Ib)) is preferably 30 mol % or more, more preferably 50 mol % or more, further preferably 80 mol % or more, based on the total amount of all the phenol monomers (these phenols are sometimes referred to as phenolic starting raw materials.).
A polymer obtained by oxidative polymerization of a substituted phenol compound represented by the above-mentioned formula (Ia) of the present invention, is a polymer having repeating units of the following basic structural formula (V) and/or the following basic structural formula (VI). 
In the phenylene rings of the formulae (V) and (VI) above, substituents are omitted.
A polymer obtained by oxidative polymerization of a 2,6-di-substituted phenol compound represented by the above-mentioned formula (Ib) of the present invention, is a polymer having a poly(1,4-phenylene oxide) structure having repeating units of the following basic structural formula (VII). 
The number-average degree of polymerization of the polymer of the present invention is generally 3 or more. When the value of the number-average molecular weight is represented by A, and the value of the molecular weight of a phenolic starting raw material (in the case of a mixture, average molecular weight) is represented by B, the number-average degree of polymerization is A/(B-2). The number-average degree of polymerization is preferably from 3 to 10,000, more preferably from 4 to 1,000, further preferably from 5 to 500.
The polymer of the present invention is preferably a crystalline polymer manifesting a crystal melting point of 5 J/g or more at xe2x88x92100xc2x0 C. or more, after melting-cooling. In this polymer, the crystal melting point is measured as described below. Namely, differential scanning calorie analysis is carried out under an argon atmosphere, and first, the polymer is cooled to xe2x88x92100xc2x0 C. at 10xc2x0 C./min, then, the temperature is raised at 10xc2x0 C./min from xe2x88x92100xc2x0 C. to the temperature at which the polymer is completely melted. Then, the polymer is cooled again to xe2x88x92100xc2x0 C., and if an endothermic peak of 5 J/g or more is found at xe2x88x92100xc2x0 C. or more, in raising the temperature again at 10xc2x0 C./min from xe2x88x92100xc2x0 C. to the temperature at which the polymer is completely melted, this peak top temperature is referred to as crystal melting point, and the peak area is referred to as crystal melting calorie.
The crystal melting point of this polymer is generally xe2x88x92100xc2x0 C. or more, preferably xe2x88x92100xc2x0 C. or more and less than 300xc2x0 C., more preferably xe2x88x9250xc2x0 C. or more and less than 150xc2x0 C., further preferably xe2x88x9240xc2x0 C. or more and less than 100xc2x0 C., further preferably 0xc2x0 C. or more and less than 100xc2x0 C., particularly preferably 0xc2x0 C. or more and less than 80xc2x0 C. The crystal melting calorie is generally 5 J/g or more, preferably 7 J/g or more, more preferably 10 J/g or more, further preferably 15 J/g or more, further preferably 20 J/g or more, particularly preferably 30 J/g or more. The upper limit of the heat generation peak calorie in crystallization is generally 200 J/g.
The polymer of the present invention contains substantially no gel portion preferably. No existence of a gel portion can be confirmed, e.g., by dissolution of 1 mg of a polymer in 1 ml of 1,2-dichlorobenzene at 150xc2x0 C. The phrase xe2x80x9ccontains substantially no gel portionxe2x80x9d means that the proportion of gel portions contained in a polymer, is preferably 5 wt % or less, further preferably 2 wt % or less, and most preferably, means no gel portion contained.
A method for producing the polymer of the present invention is described in detail below.
The above-mentioned oxidative polymerization of phenolic starting raw materials, may be electrolytic oxidative polymerization, however, oxidative polymerization using a catalyst and oxidizer, is preferable from the standpoint of energy saving.
As examples of the catalyst, a monodentate ligand/transition metal complex described in JP-B-36-18692 (xe2x80x9cJP-Bxe2x80x9d means examined Japanese patent publication), JP-A-10-53649 (xe2x80x9cJP-Axe2x80x9d means unexamined Japanese patent publication), and Japanese Patent Application No. 2000-119826; a bidentate ligand/transition metal complex described in JP-A-10-168179 and Japanese Patent Application No. 2000-121512; a tridentate ligand/transition metal complex described in JP-A-9-144449, 10-45904, 9-324040, Japanese Patent No. 3035559, and JP-A-2000-336166; a quadridentate or a quinquedentate ligand/transition metal complex described in JP-A-8-53545 and 9-324042; a hexadentate or more ligand/transition metal complex described in JP-A-9-324043; a metallocene complex described in JP-A-9-324045; metal fine particles described in JP-A-8-208813; oxidation enzymes described in JP-A-9-107984, and the like are preferable. Further preferable are a monodentate ligand/transition metal complex, a bidentate ligand/transition metal complex, a tridentate ligand/transition metal complex and a quadridentate ligand/transition metal complex, and particularly preferable is a tridentate ligand/transition metal complex. The use amount of these catalysts can be applied, replacing the use amounts for a phenol compound described in the above respectively with the use amounts for the above-mentioned phenolic starting raw materials. Further, also reaction conditions such as a reaction solvent, use amount of a reaction solvent, reaction temperature, and the like, which is described in the above respectively can be applied.
As the oxidizing agent, oxygen or a peroxide is preferable. Oxygen may be mixed with an inert gas, or may be fed in the form of air. As the peroxide, hydrogen peroxide, t-butyl hydroperoxide, di-t-butyl peroxide, cumene hydroperoxide, dicumyl peroxide, peracetic acid, perbenzoic acid, and the like, may be exemplified. Further preferable oxidizing agent is oxygen or hydrogen peroxide. The amount of the oxidizing agent used, is not restricted, however, when oxygen is used, it is generally used in 0.5 equivalent to large excess, and when a peroxide is used, it is generally used in 0.5 to 3 equivalent per phenol.
The oxidation polymer of a substituted phenol of the present invention can be used alone or in the form of a composition with other polymer and/or modifier. As the polymer component of the composition, specifically exemplified examples include polyolefins such as polyethylene, polypropylene, polystyrene, polyvinyl chloride, polymethyl methacrylate, polyvinyl acetate, polyacrylonitrile, and copolymers thereof, and the like; polyethers such as polyoxymethylene, polyphenylene oxide, poly(2,6-dimethyl-1,4-phenylene oxide), poly(2,5-dimethyl-1,4-phenylene oxide), and copolymer thereof, and the like; polyesters such as polyethylene terephthalate, polybutylene terephthalate, poly(ethylene-2,6-dinaphthalate), poly(4-oxybenzoate), poly(2-oxy-6-naphthalate), and copolymers thereof, and the like; polyamides such as nylon 6, nylon 66, and the like; polycarbonates; polyphenylene sulfides; polysulfones; polyether sulfones; polyether ether ketones; polyimides; polyether imides; thermosetting polymers such as a phenol resin, an urea resin, a melamine resin, an epoxy resin, and the like. As the modifier component of the composition, specifically exemplified examples include stabilizers such as 2,6-di-t-butylphenol derivative, 2,2,6,6-tetramethylpiperidine, and the like; flame retardants such as polyhalides, phosphates, and the like; surfactants; flow modifiers.
The novel oxidation polymer of substituted phenols of the present invention has a substituent composed of a large number of carbon atoms, and it can be crystallized at a specific temperature. When solubility based on a side chain group of the polymer, is utilized, the use in a polymer alloy compatibilizer, and the like, is expected. When crystallinity based on a side chain group thereof, is utilized, the use in a thermoplastic elastomer and the like, is expected. Further, when optical property is utilized, the use in display materials, thermosensors, and the like, is expected. Accordingly the industrial significance thereof is high. The novel oxidation polymer of a substituted phenol can be produced by a method that uses no formalin, and that is a comparatively low-temperature reaction including normal temperature, and that is an environmentally mild method whose by-product is water only.
The present invention is explained in more detail based on the following examples, but the scope of the present invention is not limited by these examples.